Carpet with hydrophobic surface finish

ABSTRACT

The present invention relates to a treated carpet comprising a partial or complete coating on a carpet surface, wherein the coating comprises 5 to 100% by weight of a hydrophobic compound, based on the total weight of the coating, selected from a cyclic or acyclic alcohol which is substituted with at least two hydrophobic groups.

FIELD OF THE INVENTION

Hydrophobic substituted alcohols are employed in surface finish coatingsto provide surface effects to carpet articles.

BACKGROUND OF THE INVENTION

Various compositions are known to be useful as treating agents toprovide surface effects to substrates. Surface effects includerepellency to moisture, soil and stain resistance, and other effectswhich are particularly useful for fibrous substrates such as fibers,fabrics, textiles, carpets, paper, leather and other such substrates.Many such treating agents are partially fluorinated polymers orcopolymers.

Fluorinated polymer compositions having utility as fibrous substratetreating agents generally contain pendant perfluoroalkyl groups of threeor more carbon atoms, which provide oil- and water-repellency when thecompositions are applied to fibrous substrate surfaces. Theperfluoroalkyl groups are generally attached by various connectinggroups to polymerizable groups not containing fluorine. The resultingmonomer is then generally copolymerized with other monomers which conferadditional favorable properties to the substrates. Various specializedmonomers may be incorporated to impart improved cross-linking, latexstability and substantivity. Since each ingredient may impart somepotentially undesirable properties in addition to its desirable ones,the specific combination is directed to the desired use. These polymersare generally marketed as aqueous emulsions for easy application to thefibrous substrates.

Various attempts have been made to increase the oil- andwater-repellency imparted to the substrate and its durability whilereducing the amount of fluorinated polymer required, i.e., boost theefficiency or performance of the treating agent. One method is toincorporate blocked isocyanates or melamine resins. However, onlylimited amounts can be used because these ingredients tend to adverselyaffect the handle (the feel) of the fibrous substrate. Another approachemploys use of various extender polymers. These are typicallyhydrocarbon polymers in aqueous emulsions, which are blended with thefluorinated polymer emulsion before application to the substrate.

U.S. Pat. No. 7,820,745 discloses aqueous water- and oil-repellentcompositions containing a fluorinated copolymer in aqueous medium and asorbitan ester used in small amounts to act as a surfactant. Thereference does not, however, show the surface effect benefits of usinghydrophobic sorbitan esters or other hydrophobic ester alcohol compoundson carpet substrates.

BRIEF SUMMARY OF THE INVENTION

There is a need for surface effect compositions which providehydrophobicity performance to carpet with improved fluorine efficiency.The present invention provides such a composition.

The present invention comprises a treated carpet comprising a partial orcomplete coating on a carpet surface, wherein the carpet is made ofnatural fibers, nylon, acrylics, aromatic polyamides, polyesters,polyacrylonitrile, or polyacrylonitrile copolymers, wherein the coatingcomprises 5 to 100% by weight of a hydrophobic compound, based on thetotal solids weight of the coating, selected from a cyclic or acyclicalcohol which is substituted with at least two —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic alcohol is selected from a pentaerythritol, asaccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid,or aldonic acid lactone; wherein each n is independently 0 to 20; each mis independently 0 to 20; m+n is greater than 0; each R¹ isindependently a linear or branched alkyl group having 5 to 29 carbonsoptionally comprising at least 1 unsaturated bond; and each R² isindependently —H, a linear or branched alkyl group having 6 to 30carbons optionally comprising at least 1 unsaturated bond.

The present invention further comprises a method of imparting a surfaceeffect to a carpet comprising contacting a carpet surface with a coatingto form a partially or completely treated carpet, wherein the carpet ismade of natural fibers, nylon, acrylics, aromatic polyamides,polyesters, polyacrylonitrile, or polyacrylonitrile copolymers, whereinthe coating comprises 5 to 100% by weight of a hydrophobic compound,based on the total solids weight of the coating, selected from a cyclicor acyclic alcohol which is substituted with at least two —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic alcohol is selected from a pentaerythritol,saccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid,or aldonic acid lactone; wherein each n is independently 0 to 20; each mis independently 0 to 20; m+n is greater than 0; each R¹ isindependently a linear or branched alkyl group having 5 to 29 carbonsoptionally comprising at least 1 unsaturated bond; each R² isindependently —H, a linear or branched alkyl group having 6 to 30carbons optionally comprising at least 1 unsaturated bond.

DETAILED DESCRIPTION OF THE INVENTION

Trademarks are indicated herein by capitalization.

The present invention provides treated carpet articles having improvedwater repellency, oil or stain repellency, and/or other surface effects.The treated articles provide enhanced performance compared totraditional non-fluorinated commercially available treatment agents. Thecoating materials of the present invention can be derived frombio-sourced materials. The coatings formed are durable, by which ismeant that the coatings are lasting films that are not readily removedby water or cleaning agents. In one aspect, the coatings are not solubleor dispersable in water or cleaning agents once they are dry, and inanother aspect, the coatings withstand multiple cleanings without lossof performance.

The present invention comprises a treated carpet comprising a partial orcomplete coating on a carpet surface, wherein the carpet is made ofnatural fibers, nylon, acrylics, aromatic polyamides, polyesters,polyacrylonitrile, or polyacrylonitrile copolymers, wherein the coatingcomprises 5 to 100% by weight of a hydrophobic compound, based on thetotal solids weight of the coating, selected from a cyclic or acyclicalcohol which is substituted with at least two —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic alcohol is selected from a pentaerythritol, asaccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid,or aldonic acid lactone; wherein each n is independently 0 to 20; each mis independently 0 to 20; m+n is greater than 0; each R¹ isindependently a linear or branched alkyl group having 5 to 29 carbonsoptionally comprising at least 1 unsaturated bond; and each R² isindependently —H, a linear or branched alkyl group having 6 to 30carbons optionally comprising at least 1 unsaturated bond. Thesehydrophobic compounds can contain only EO groups, only PO groups, ormixtures thereof. These compounds can also be present as a tri-blockcopolymer designated PEG-PPG-PEG (polyethylene glycol-polypropyleneglycol-polyethylene glycol), for example. In one embodiment, n+m is 1 to20; in another embodiment, n and m are independently 0 to 15 and n+m is1 to 15; and in a third embodiment, n and m are independently 0 to 12and n+m is 1 to 12.

The hydrophobic compound may be a multi-ester alcohol having at leasttwo hydrophobic substitutions, which originates from a polyol orpolycarboxylic acid compound. Examples of suitable polyols include butare not limited to cyclic or acyclic sugar alcohols, or pentaerythritolsincluding dipentaerythritol. Suitable polycarboxylic acid compoundsinclude citric acid. The cyclic or acyclic sugar alcohol is selectedfrom a saccharide, reduced sugar, aminosaccharide, aldonic acid, aldonicacid lactone. Mixtures of these compounds may also be used. Thehydrophobic compounds are substituted with at least two —R¹; —C(O)R¹;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; or mixtures thereof. Such asubstitution lends hydrophobic character to the monomer, and to thepolymer molecules. In one embodiment, the hydrophobic compound issubstituted with at least three —R¹; —C(O)R¹;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; or mixtures thereof.

These substituted compounds can be made by the reaction of a sugaralcohol with at least one fatty acid or alkoxylated fatty acid, such asby esterification of a fatty acid; or by esterification of apolycarboxylic acid with a long-chain alcohol. Examples of such sugaralcohols include but are not limited to aldoses and ketoses such asthose compounds derived from tetroses, pentoses, hexoses, and heptoses.Specific examples include glucose, 1,4-anhydro-D-glucitol,2,5-anhydro-D-mannitol, 2,5-anhydro-L-iditol, isosorbide, sorbitan,glyceraldehyde, erythrose, threitol, glucopyranose, mannopyranose,talopyranose, allopyranose, altropyranose, idopyranose, gulopyranose,glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol,galactitol, fucitol, iditol, inositol, pentaerythritol,dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonicacid, galactaric acid, ascorbic acid, citric acid, gluconic acidlactone, glyceric acid lactone, xylonic acid lactone, glucosamine,galactosamine, or mixtures thereof.

Suitable fatty acids include, but are not limited to, caprylic acid,capric acid, lauric acid, mysteric acid, palmitic acid, stearic acid,arachidic acid, behenic acid, lignoceric acid, palmitoleic acid,lineolic acid, oleic acid, erucic acid, alkoxylated versions of theseacids, and mixtures thereof.

In one embodiment, R¹ is a linear or branched alkyl group having 11 to29 carbons, and in another embodiment, R¹ is a linear or branched alkylgroup having 17 to 21 carbons. In one embodiment, R² is a linear orbranched alkyl group having 12 to 30 carbons, in another embodiment, R²is a linear or branched alkyl group having 18 to 30 carbons, and inanother embodiment, R² is a linear or branched alkyl group having 18 to22 carbons. In one embodiment, the fatty acid or long-chain alcoholsubstitution of the cyclic or acyclic sugar alcohols has a melting pointof at least −59° C. In another embodiment, it has a melting point of atleast 0° C., and in a third embodiment, it has a melting point of atleast 40° C.

In one embodiment, the hydrophobic compound is selected from Formulas(Ia), (Ib), or (Ic):

wherein each R is independently —H; —R¹; —C(O)R¹;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; each n is independently 0 to 20;each m is independently 0 to 20; m+n is greater than 0; r is 1 to 3; ais 0 or 1; p is independently 0 to 2; provided that a is 0 when r is 3;each R¹ is independently a linear or branched alkyl group having 5 to 29carbons optionally comprising at least 1 unsaturated bond; each R² isindependently —H, or a linear or branched alkyl group having 6 to 30carbons optionally comprising at least 1 unsaturated bond; provided whenFormula (Ia) is chosen, then at least one R is —H and at least one R isa —R¹; —C(O)R¹; —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; each R⁴ is independently —H, alinear or branched alkyl group having 6 to 30 carbons optionallycomprising at least 1 unsaturated bond, or combinations thereof;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; provided when Formula (Ib) ischosen, then at least one R or R⁴ is —H; and at least two of R or R⁴ area linear or branched alkyl group optionally comprising at least 1unsaturated bond, or combinations thereof;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; and each R¹⁹ is —H, —C(O)R¹, or—CH₂C[CH₂OR]₃, provided when Formula (Ic) is chosen, then at least oneR¹⁹ or R is —H; and at least two of R¹⁹ or R are —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹.

Where the hydrophobic compound is Formula (Ia), any suitable substitutedreduced sugar alcohol may be employed, including esters of 1,4-sorbitan,esters of 2,5-sorbitan, and esters of 3,6-sorbitan. In one embodiment,the hydrophobic compound is selected from Formula (a) to be Formula(Ia′):

wherein R is further limited to —H; —R¹; or —C(O)R¹ and at least two Rgroups are —C(O)R¹ or R¹. Compounds used to form residues of Formula(Ia′), having at least one of R is —H and at least one R is selectedfrom —C(O)R¹, are commonly known as alkyl sorbitans. These sorbitans canbe di-substituted or tri-substituted with —C(O)R¹. It is known thatcommercially available sorbitans, such as SPAN, contain a mixture of thevarious sorbitans ranging from where each R is H (un-substituted), andsorbitans where each R is —C(O)R¹ (fully substituted); wherein R¹ is alinear or branched alkyl group having 5 to 29 carbons; and mixtures ofvarious substitutions thereof. The commercially available sorbitans mayalso include amounts of sorbitol, isosorbide, or other intermediates orbyproducts.

In one embodiment, at least two R groups are —C(O)R¹, and R¹ is a linearbranched alkyl group having 5 to 29 carbons. In another embodiment, R¹is a linear or branched alkyl group having 7 to 21 carbons, and in athird embodiment, R¹ is a linear or branched alkyl group having 11 to 21carbons. Preferred compounds used to form these residues include mono-,di-, and tri-substituted sorbitans derived from caprylic acid, capricacid, lauric acid, mysteric acid, palmitic acid, stearic acid, arachidicacid, behenic acid, lignoceric acid, and mixtures thereof. Particularlypreferred compounds include di- and tri-substituted sorbitan stearatesor sorbitan behenins.

Optionally, R¹ is a linear or branched alkyl group having 5 to 29carbons comprising at least 1 unsaturated bond. Examples of compounds ofFormula (Ia) wherein at least two R groups are selected from —C(O)R¹;and R¹ contains least 1 unsaturated bond, include, but are not limitedto, sorbitan trioleate (i.e., wherein R¹ is —C₇H₁₄CH═CHC₈H₁₇). Otherexamples but are not limited to include di- and tri-substitutedsorbitans derived from palmitoleic acid, lineolic acid, arachidonicacid, and erucic acid.

In one embodiment, a compound of Formula (Ia) is employed, wherein atleast two R groups are independently —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²or —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹. Compounds of Formula (Ia),wherein at least two R groups are —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R² or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, wherein each m is independently 0to 20, each n is independently 0 to 20, and n+m is greater than 0 areknown as polysorbates and are commercially available under the tradenameTWEEN. These polysorbates can be di-substituted or tri-substituted withalkyl groups R¹ or R². It is known that commercially availablepolysorbates contain a mixture of the various polysorbates ranging fromwhere each R² is H (unsubstituted), and polysorbates where each R¹ is alinear or branched alkyl group having 5 to 29 carbons (fullysubstituted); and mixtures of various substitutions thereof. Examples ofcompounds of Formula (Ia) include polysorbates such as polysorbatetristearate and polysorbate monostearate. Examples of compounds ofFormula (Ia) wherein m+n is greater than 0, and wherein R¹ comprises atleast 1 unsaturated bond, but not limited to, polysorbate trioleate(wherein R¹ is C₇H₁₄CH═CHC₈H₁₇) and are sold commercially under the namePolysorbate 80. Reagents may include mixtures of compounds havingvarious values for R, R¹, and R², and may also include mixtures ofcompounds where R¹ comprises at least one unsaturated bond withcompounds where R¹ is fully saturated.

Compounds of Formula (Ib) are known as alkyl citrates. These citratescan be present as a di-substituted or tri-substituted with alkyl groups.It is known that commercially available citrates contain a mixture ofthe various citrates as well as citric acids from where R and each R⁴ is—H, ranging to citrates where each R⁴ is a linear or branched alkylgroup having 6 to 30 carbons optionally comprising at least 1unsaturated bond; and mixtures of various substitutions thereof.Mixtures of citrates having various values for R¹, R², and R⁴ may beused, and may also include mixtures of compounds where R¹ comprises atleast one unsaturated bond with compounds where R¹ is fully saturated.Alkyl citrates are also commercially available wherein m+n is greaterthan 0, R⁴ is —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹ and are present in the varioussubstitutions from wherein R and each R² is H to wherein each R¹ and/orR² is a linear or branched alkyl group having 5 to 30 carbons optionallycomprising at least 1 unsaturated bond. Examples of compounds of Formula(Ib) include, but are not limited to, trialkyl citrates.

Compounds of Formula (Ic) are known as pentaerythriol esters. Thesepentaerythriol esters can be present as a di-substituted ortri-substituted with alkyl groups. Preferred compounds used to form X ofFormula (Ic) are dipentaerythriol esters, where R¹⁹ is —CH₂C[CH₂OR]₃. Itis known that commercially available pentaerythriol esters contain amixture of the various pentaerythriol esters where R¹⁹ and each R is —H,ranging to pentaerythriol esters where each R is —C(O)R¹, and R¹ is alinear or branched alkyl group having 5 to 29 carbons optionallycomprising at least 1 unsaturated bond; and mixtures of varioussubstitutions thereof. The pentaerythriol esters also may containcompounds with mixtures of different chain lengths for R, or mixtures ofcompounds where R¹ comprises at least one unsaturated bond withcompounds where R¹ is fully saturated.

Compounds of Formulas (Ia), (Ib), and (Ic) can all be bio-based derived.By “bio-based derived”, it is meant that at least 10% of the materialcan be produced from non-crude oil sources, such as plants, othervegetation, and tallow. In one embodiment, the hydrophobic compound isfrom about 10% to 100% bio-based derived. In one embodiment, hydrophobiccompound is from about 35% to 100% bio-based derived. In anotherembodiment, hydrophobic compound is from about 50% to 100% bio-basedderived. In one embodiment, hydrophobic compound is from about 75% to100% bio-based derived. In one embodiment, hydrophobic compound is 100%bio-based derived. The average OH value of the hydrophobic compounds canrange from just greater than 0 to about 230. In one embodiment, theaverage OH value is from about 10 to about 175, and in anotherembodiment, the average OH value is from about 25 to about 140.

The coating on the carpet surface comprises 5 to 100% by weight of thehydrophobic compound, based on the total solids weight of the coating.In a second aspect, the coating on the carpet surface comprises 20 to100% by weight of the hydrophobic compound; and in a third aspect, 50 to100% by weight of the hydrophobic compound based on the total solidsweight of the coating. The term “solids weight of the coating”, is usedto mean the sum of the coating components that would remain once theaqueous, solvent, or other liquid components evaporated. In other words,it is the sum of the non-aqueous, non-solvent, and non-volatilecomponents of the coating. The coating may further comprise aqueous ororganic solvents, polymer resins, coating bases that contain polymerresins, pigments, functional additives, surfactants, and hydrophobicsurface effect agents.

In one embodiment, the hydrophobic compound is combined with ahydrophobic surface effect agent to extend or improve the performance ofthe surface effect agent. In this case, the hydrophobic surface effectagents may be used from about 5:95 to about 95:5 in one aspect; fromabout 10:90 to 90:10 in a second aspect; and from about 20:80 to 80:10in a third aspect, based on the total solids weight of the coating.Hydrophobic surface effect agents provide surface effects such as noiron, easy to iron, shrinkage control, wrinkle free, permanent press,moisture control, softness, strength, anti-slip, anti-static, anti-snag,anti-pill, stain repellency, stain release, soil repellency, soilrelease, water repellency, oil repellency, odor control, antimicrobial,sun protection, and similar effects. Such materials can be in the formof hydrophobic non-fluorinated cationic acrylic polymers, hydrophobicnon-fluorinated anionic acrylic polymers, hydrophobic non-fluorinatednonionic acrylic polymers, partially fluorinated urethanes, hydrophobicnon-fluorinated urethanes, cationic partially fluorinated acrylicpolymers or copolymers, nonionic partially fluorinated acrylic polymersor copolymers, partially fluorinated acrylamide polymers or copolymers,fluorinated phosphates, fluorinated or non-fluorinated organosilanes,silicones, waxes, including parafins, and mixtures thereof. Some stainrelease and soil release agents are hydrophilic and include compoundssuch as polymethyl acrylates. These compounds may also be combined withthe hydrophobic compounds, in the ratios stated above, as surface effectagents.

Superior properties, along with desirable properties of low yellowingand good durability, are imparted to articles by the combination of thehydrophobic compounds to hydrophobic surface effect agents beforeapplication to the articles. These combined blends are applied to thearticles in the form of a dispersion in water or other solvent eitherbefore, after or during the application of other treatment chemicals.

Of particular interest are fluorinated polymers useful as hydrophobicsurface effect agents to provide repellency properties to the surface oftreated substrates. These include fluorochemical compounds or polymerscontaining one or more fluoroaliphatic groups (designated here as R_(f)groups) which are fluorinated, stable, inert, and non-polar, preferablysaturated, monovalent, and both oleophobic and hydrophobic. The R_(f)groups contain at least 3 carbon atoms, preferably 3 to 20 carbon atoms,more preferably 4 to 12 carbon atoms, and most preferably about 4 toabout 6 carbon atoms. The R_(f) groups may contain straight or branchedchain or cyclic fluorinated alkylene groups or combinations thereof. Theterminal portion of the R_(f) groups is preferably a perfluorinatedaliphatic group of the formula C_(n)F_(2n+1) wherein n is from about 3to about 20. Examples of fluorinated polymer treating agents areCAPSTONE and ZONYL available from The Chemours Company, Wilmington,Del.; ASAHI GARD from Asahi Glass Company, Ltd., Tokyo, Japan; UNIDYNEfrom Daikin America, Inc., Orangeburg, N.Y.; SCOTCHGARD from 3M Company,St. Paul, Minn.; and NANO TEX from Nanotex, Emeryville, Calif.

Examples of such fluorinated polymers include R_(f)-containingpolyurethanes and poly(meth)acrylates. Especially preferred arecopolymers of fluorochemical (meth)acrylate monomers with aco-polymerizable monovinyl compound or a conjugated diene. Theco-polymerizable monovinyl compounds include alkyl (meth)acrylates,vinyl esters of aliphatic acids, styrene and alkyl styrene, vinylhalides, vinylidene halides, alkyl esters, vinyl alkyl ketones, andacrylamides. The conjugated dienes are preferably 1,3-butadienes.Representative compounds within the preceding classes include themethyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, isoamyl,2-ethylhexyl, octyl, decyl, lauryl, cetyl, and octadecyl acrylates andmethacrylates; vinyl acetate, vinyl propionate, vinyl caprylate, vinyllaurate, vinyl stearate, styrene, alpha methyl styrene, p-methylstyene,vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride,vinylidene chloride, allyl heptanoate, allyl acetate, allyl caprylate,allyl caproate, vinyl methyl ketone, vinyl ethyl ketone, 1,3-butadiene,2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, isoprene,N-methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate,glycidyl methacrylate, amine-terminated (meth)acrylates, andpolyoxy(meth)acrylates.

Hydrophobic non-fluorinated acrylic polymers include copolymers ofmonovinyl compounds, including alkyl (meth)acrylates, vinyl esters ofaliphatic acids, styrene and alkyl styrene, vinyl halides, vinylidenehalides, alkyl esters, vinyl alkyl ketones, and acrylamides. Theconjugated dienes are preferably 1,3-butadienes. Representativecompounds within the preceding classes include the methyl, propyl,butyl, 2-hydroxypropyl, 2-hydroxyethyl, isoamyl, 2-ethylhexyl, octyl,decyl, lauryl, cetyl, and octadecyl acrylates and methacrylates; vinylacetate, vinyl propionate, vinyl caprylate, vinyl laurate, vinylstearate, styrene, alpha methyl styrene, p-methylstyene, vinyl fluoride,vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride,allyl heptanoate, allyl acetate, allyl caprylate, allyl caproate, vinylmethyl ketone, vinyl ethyl ketone, 1,3-butadiene,2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, isoprene,N-methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate,glycidyl methacrylate, amine-terminated (meth)acrylates, andpolyoxy(meth)acrylates.

Hydrophobic non-fluorinated urethanes include, for example, urethanessynthesized by reacting an isocyanate compound with the hydrophobiccompounds described above as an alcohol reagent. These compounds aredescribed in US2014/0295724 and US2016/0090508. Hydrophobicnon-fluorinated nonionic acrylic polymers include, for example, polymersmade by polymerizing or copolymerizing an acrylic ester of thehydrophobic compounds described above. Such compounds are described inUS2016/0090686.

The coatings of the present invention applied to the carpet surfaceoptionally further comprise a blocked isocyanate to promote durability,added after copolymerization (i.e., as a blended isocyanate). An exampleof a suitable blocked isocyanate is PHOBOL XAN available from HuntsmanCorp, Salt Lake City, Utah Other commercially available blockedisocyanates are also suitable for use herein. The desirability of addinga blocked isocyanate depends on the particular application for thecopolymer. For most of the presently envisioned applications, it doesnot need to be present to achieve satisfactory cross-linking betweenchains or bonding to fibers. When added as a blended isocyanate, amountsup to about 20% by weight are added.

The coating composition of the present invention optionally furthercomprises additional components such as additional treating agents orfinishes to achieve additional surface effects, or additives commonlyused with such agents or finishes. Such additional components comprisecompounds or compositions that provide surface effects such as no iron,easy to iron, shrinkage control, wrinkle free, permanent press, moisturecontrol, softness, strength, anti-slip, anti-static, anti-snag,anti-pill, stain repellency, stain release, soil repellency, soilrelease, water repellency, oil repellency, odor control, antimicrobial,sun protection, and similar effects. One or more such treating agents orfinishes can be combined with the blended composition and applied to thefibrous substrate. Other additives commonly used with such treatingagents or finishes may also be present such as surfactants, pHadjusters, cross linkers, wetting agents, and other additives known bythose skilled in the art. Further, other extender compositions areoptionally included to obtain a combination of benefits.

In one embodiment, the present invention is method of imparting asurface effect to a carpet comprising contacting a carpet surface with acoating to form a partially or completely treated carpet, wherein thecarpet is made of natural fibers, nylon, acrylics, aromatic polyamides,polyesters, polyacrylonitrile, or polyacrylonitrile copolymers, whereinthe coating comprises 5 to 100% by weight of a hydrophobic compound,based on the total solids weight of the coating, selected from a cyclicor acyclic alcohol which is substituted with at least two —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic alcohol is selected from a pentaerythritol,saccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid,or aldonic acid lactone; wherein each n is independently 0 to 20; each mis independently 0 to 20; m+n is greater than 0; each R¹ isindependently a linear or branched alkyl group having 5 to 29 carbonsoptionally comprising at least 1 unsaturated bond; each R² isindependently —H, a linear or branched alkyl group having 6 to 30carbons optionally comprising at least 1 unsaturated bond. Specificrepresentative examples of carpet compositions include but are notlimited to natural fibers, such as cotton, wool, silk, jute, sisal, andother cellulosics; nylon including nylon 6, nylon 6,6 and aromaticpolyamides; polyesters including poly(ethyleneterephthalate) orpoly(trimethyleneterephthalate) such as Triexta; polyacrylonitrile orpolyacrylonitrile copolymers. The contacting step may occur by applyingthe hydrophobic compound as a solid, or by liquid carrier. When appliedby liquid carrier, the hydrophobic compound may be in the form of anaqueous solution, aqueous dispersion, organic solvent solution ordispersion, or cosolvent solution or dispersion. The contacting step mayoccur by any conventional method, including but not limited to spraying,rolling, padding, brushing, sprinkling, dipping, dripping, tumbling,screen printing, or other mechanical means known in the technology totreat fibrous substrates.

In one aspect, the method further comprises the step of heating thepartially or completely coated carpet. For example, the hydrophobicagent may be applied alone or in liquid carrier, and the treated carpetmay be heated to melt, flow, dry, or otherwise fix the hydrophobic agentonto the carpet surface. The final coating on the carpet surface will bea solidified, lasting, permanent coating. In another aspect, the methodfurther comprises the step of solidifying the coating by drying,cooling, or allowing to cool. In one embodiment, the solid hydrophobiccompound is sprinkled onto the carpet surface, and the treated carpet isheated to fix the hydrophobic compound onto the surface. The liquidcarrier, if used, may be dried by heating or air drying to allow forevaporation of the liquid carrier, thus leaving a permanent solidcoating.

Specifically, the treated carpets of the present invention are usefulfor providing articles with enhanced surface properties, especiallydurability of oil-, water- and soil-repellency, while reducing oreliminating the amount of fluorinated compounds employed. The repellencyproperty is effective with a variety of other surface effects.

TEST METHODS

All solvents and reagents, unless otherwise indicated, were purchasedfrom Sigma-Aldrich, St. Louis, Mo., and used directly as supplied.Sorbitan tristearate was obtained from Croda, East Yorkshire, Englandand DuPont Nutrition & Health, Copenhagen, Denmark. WITCOLATE WAQE isavailable from Akzo Nobel, Chicago, Ill.

The following tests were employed in evaluating the examples herein.

Test Method 1—Accelerated Soiling Test

A drum mill (on rollers) was used to tumble synthetic soil onto thecarpet. Synthetic soil was prepared as described in AATCC Test Method123-2000, Section 8. Synthetic soil, 3 g, and 1 liter of clean nylonresin beads ( 3/16 inch (0.32-0.48 cm) diameter ZYTEL 101 nylon resinbeads, commercially available from E. I. du Pont de Nemours and Company,Wilmington, De., were placed into a clean, empty canister. The canisterlid was closed and sealed and the canister rotated on rollers for 5minutes. The soil-coated beads were removed from the canister.

Total carpet sample size was 8×24 inch (20.3×60.9 cm). One test item andone control item were tested simultaneously. The carpet pile of allsamples was laid in the same direction. Strong adhesive tape was placedon the backside of the carpet pieces to hold them together. The carpetsamples were placed in the clean, empty drum mill with the tufts facingtoward the center of the drum. The carpet was held in place in the drummill with rigid wires. Soil-coated resin beads, 250 ml, and 250 ml of5/16 in. diameter ball bearings (0.79 cm.), prepared as described above,were placed into the drum mill. The drum mill lid was closed and sealed.The drum was run on the rollers for 2½ minutes at about 105 rpm. Therollers were stopped and the direction of the drum mill reversed. Thedrum was run on the rollers for an additional 2½ minutes at about 105rpm. The carpet samples were removed and vacuumed uniformly with 5passes in each direction to remove excess dirt. The Delta (Δ) E colordifference for the soiled carpet was measured for the test and controlitems versus the unsoiled carpet for each item.

Color measurement of each carpet was conducted on the carpet followingthe accelerated soiling test. For each test sample and control samplethe color of the carpet was measured, the sample was soiled, and thecolor of the soiled carpet was measured. The Δ E was the differencebetween the color of the soiled and unsoiled samples. Color differencewas measured on each item, using a Minolta Chroma Meter CR 410 (MinoltaCorporation, Ramsey, N.J.). Color readings were taken at three differentareas on the carpet sample, and the average ΔE was recorded.

The control carpet for each test item was of the same color andconstruction as the test item.

Δ Δ E was calculated by subtracting the Δ E of the control (untreated)carpet from the Δ E of the test item. A larger negative value for Δ Δ Eindicated that the test carpet had better performance and less soilingthan the control. A larger positive value for Δ Δ E indicated that thetest carpet had poorer performance and soiled more than the control.Note that, although different untreated samples may yield slightlydifferent L ratings, the test samples are compared to the untreatedcontrol sample that is tested simultaneously with the test sample.

Test Method 2—Oil Repellency

Oil repellency was measured according to AATCC Test Method 118. Highervalues indicate increased oil repellency.

The treated samples were tested for oil repellency by a modification ofAATCC standard Test Method No. 118, conducted as follows. A substratetreated with an aqueous dispersion of polymer as previously described,is conditioned for a minimum of 2 hours at 23 C and 20% relativehumidity and 65 C and 10% relative humidity. A series of organicliquids, identified below in Table 1, are then applied dropwise to thesamples. Beginning with the lowest numbered test liquid (RepellencyRating No. 1), one drop (approximately 5 mm in diameter or 0.05 mLvolume) is placed on each of three locations at least 5 mm apart. Thedrops are observed for 30 seconds. If, at the end of this period, two ofthe three drops are still spherical in shape with no wicking around thedrops, three drops of the next highest numbered liquid are placed onadjacent sites and similarly observed for 30 seconds. The procedure iscontinued until one of the test liquids results in two of the threedrops failing to remain spherical to hemispherical, or wetting orwicking occurs.

The oil repellency rating is the highest numbered test liquid for whichtwo of the three drops remained spherical to hemispherical, with nowicking for 30 seconds. In general, treated samples with a rating of 5or more are considered good to excellent; samples having a rating of oneor greater can be used in certain applications.

TABLE 1 Oil Repellency Test Liquids Oil Repellency Rating Test Solution1 NUJOL Purified Mineral Oil 2 65/35 Nujol/n-hexadecane by volume at 21C. 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane 7 n-octane 8n-heptane Note: NUJOL is a trademark of Plough, Inc., for a mineral oilhaving a Saybolt viscosity of 360/390 at 38 C. and a specific gravity of0.880/0.900 at 15 C.

Test Method 3—Water Repellency

The water repellency of a treated substrate was measured according toAATCC standard Test Method No. 193 and the DuPont Technical LaboratoryMethod as outlined in the TEFLON Global Specifications and QualityControl Tests information packet. The test determines the resistance ofa treated substrate to wetting by aqueous liquids. Drops ofwater-alcohol mixtures of varying surface tensions are placed on thesubstrate and the extent of surface wetting is determined visually.Place a test carpet sample on a flat, non-absorbent surface. Beginningwith the lowest numbered test liquid, carefully place one drop inseveral locations on the surface of the carpet sample. If no penetrationor wetting of the carpet at the liquid-carpet interface and no wickingaround the drop occurs, place drops of the next higher-numbered testliquid at an adjacent site on the carpet sample. Repeat this procedureuntil one of the higher number test liquids shows obvious wetting orwicking of the carpet under or around the drop within 10 seconds. Thewater repellency rating for a carpet sample is the numerical value ofthe highest-numbered test liquid which will not wet the carpet within 10seconds. Higher ratings indicate greater repellency. The composition ofwater repellency test liquids is shown in Table 2.

TABLE 2 Water Repellency Test Liquids Composition, Vol. % (IsopropylAlcohol:Distilled Water Repellency Rating Water) 1  2:98 2  5:95 3 10:904 20:80 5 30:70 6 40:60

EXAMPLES Example 1

Sorbitan tristearate, as a dry powder, is spread evenly over acommercial level loop nylon-6,6 carpet with stain resist to uniformlycover the carpet surface. Excess powder is removed by shaking the carpetuntil only a fine powder coating remained. The treated carpet is heatedto 250° F. (121° C.) until the surface temperature reaches 250° F.,cooled to room temperature, allowed to equilibrate at room temperaturefor 24-48 hours, and the carpet sample is tested according to TestMethods 1-3.

Comparative Example A

An untreated sample of commercial level loop nylon-6,6 carpet with stainresist is tested according to Test Methods 1-3.

Example 2

Into a 4-neck round bottom flask equipped with an overhead stirrer,thermocouple and condenser is added sorbitan tristearate (60.1 g) and4-methyl-2-pentanone (MIBK, 150 g). After the solution is heated to 55°C., an aqueous dispersion is prepared by adding warm water (383 g),WITCOLATE WAQE (11.4 g) and dipropylene glycol (14.8 g) at 65° C. Themixture is immersion blended (2 min), homogenized at 6000 psi, and theresulting dispersion is distilled under reduced pressure to remove thesolvent and yield a non-flammable urethane dispersion at 12.91% solidsafter cooling and filtering. The sample is applied as an aqueouscomposition by spray application to a level loop nylon-6,6 carpet withstain resist at 25% wet pick-up (wpu) and dried to a carpet facetemperature of 250° F. (121° C.). The treated carpet is tested accordingto Test Methods 1-3.

TABLE 3 Performance on Level Loop Nylon Carpet Samples Water ΔE BeforeΔE After Repellency Example Vacuum Vacuum ΔΔE Rating A 10.6 8.68 0 0 B —9.25 1.36 5 1 9.74 7.85 −0.83 4 2 — 9.28 0.63 4

Results indicate that the carpet treated by sorbitan tristearatecompounds yields high water repellency performance when compared with anuntreated sample. Further, Example 1 indicates that dry applicationspromote soil resistance in addition to water repellency.

Example 3

Example 1 was repeated, except a commercial SORONA carpet was used.

TABLE 4 Performance on SORONA Carpet Example ΔΔE Water Repellency Rating3 −5.5 1

Results indicate that the carpet treated by sorbitan tristearatecompounds yields water repellency performance and high soil resistanceperformance when compared with an untreated sample.

What is claimed is:
 1. A treated carpet comprising a partial or completecoating on a carpet surface, wherein the carpet is made of naturalfiber, nylon, acrylic, aromatic polyamide, polyester, polyacrylonitrile,or polyacrylonitrile copolymer, wherein the coating comprises 5 to 100%by weight of a hydrophobic compound, based on the total solids weight ofthe coating, selected from a cyclic or acyclic alcohol which issubstituted with at least two —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic alcohol is selected from a pentaerythritol, asaccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid,or aldonic acid lactone; wherein each n is independently 0 to 20; each mis independently 0 to 20; m+n is greater than 0; each R¹ isindependently a linear or branched alkyl group having 5 to 29 carbonsoptionally comprising at least 1 unsaturated bond; and each R² isindependently —H, a linear or branched alkyl group having 6 to 30carbons optionally comprising at least 1 unsaturated bond.
 2. Thetreated carpet of claim 1, where the hydrophobic compound is selectedfrom Formulas (Ia), (Ib), or (Ic):

wherein each R is independently —H; —R¹; —C(O)R¹;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; each n is independently 0 to 20;each m is independently 0 to 20; m+n is greater than 0; r is 1 to 3; ais 0 or 1; p is independently 0 to 2; provided that a is 0 when r is 3;each R¹ is independently a linear or branched alkyl group having 5 to 29carbons optionally comprising at least 1 unsaturated bond; each R² isindependently —H, or a linear or branched alkyl group having 6 to 30carbons optionally comprising at least 1 unsaturated bond; provided whenFormula (Ia) is chosen, then at least one R is —H and at least two Rgroups are a —R¹; —C(O)R¹; —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; each R⁴ is independently —H, alinear or branched alkyl group having 6 to 30 carbons optionallycomprising at least 1 unsaturated bond, or combinations thereof;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; provided when Formula (Ib) ischosen, then at least one R or R⁴ is —H; and at least two of R or R⁴ area linear or branched alkyl group optionally comprising at least 1unsaturated bond, or combinations thereof;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; and each R¹⁹ is —H, —C(O)R¹, or—CH₂C[CH₂OR]₃, provided when Formula (Ic) is chosen, then at least oneR¹⁹ or R is —H; and at least two of R¹⁹ or R are —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹.
 3. The treated carpet of claim 2,where the hydrophobic compound is selected from Formula (Ia) to beFormula (Ia′):

wherein R is further limited to independently —H; —R¹; or —C(O)R¹. 4.The treated carpet of claim 2, where the hydrophobic compound isselected from Formula (Ia) to be Formula (Ia′):

wherein R is further limited to independently —H;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹.
 5. The treated carpet of claim 2,where the hydrophobic compound is selected from Formula (Ib).
 6. Thetreated carpet of claim 1, where the coating further comprises ahydrophobic surface effect agent.
 7. The treated carpet of claim 6,wherein the surface effect is shrinkage control, moisture control,softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stainrepellency, stain release, soil repellency, soil release, waterrepellency, oil repellency, odor control, antimicrobial, sun protection,or acid resistance.
 8. The treated carpet of claim 6 wherein thehydrophobic surface effect agent is selected from the group consistingof non-fluorinated or fluorinated cationic acrylic polymers,non-fluorinated or fluorinated anionic acrylic polymers, non-fluorinatedor fluorinated nonionic acrylic polymers, partially fluorinatedurethanes, hydrophobic non-fluorinated urethanes, silicones, and waxes.9. The treated carpet of claim 1, where the coating comprises 20 to 100%by weight of the hydrophobic compound, based on the total solids weightof the coating.
 10. The treated carpet of claim 1, where the coatingcomprises 50 to 100% of the hydrophobic compound, based on the totalsolids weight of the coating.
 11. The treated carpet of claim 10, wherethe coating comprises 100% of the hydrophobic compound, based on thetotal weight of the coating.
 12. A method of imparting a surface effectto a carpet comprising contacting a carpet surface with a coating toform a partially or completely treated carpet, wherein the carpet ismade of natural fiber, nylon, acrylic, aromatic polyamide, polyester,polyacrylonitrile, or polyacrylonitrile copolymer, wherein the coatingcomprises 5 to 100% by weight of a hydrophobic compound, based on thetotal solids weight of the coating, selected from a cyclic or acyclicalcohol which is substituted with at least two —R¹, —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹, or mixtures thereof; where thecyclic or acyclic alcohol is selected from a pentaerythritol,saccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid,or aldonic acid lactone; wherein each n is independently 0 to 20; each mis independently 0 to 20; m+n is greater than 0; each R¹ isindependently a linear or branched alkyl group having 5 to 29 carbonsoptionally comprising at least 1 unsaturated bond; and each R² isindependently —H, a linear or branched alkyl group having 6 to 30carbons optionally comprising at least 1 unsaturated bond.
 13. Themethod of claim 12, where the hydrophobic compound is selected fromFormulas (Ia), (Ib), or (Ic):

wherein each R is independently —H; —R¹; —C(O)R¹;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; each n is independently 0 to 20;each m is independently 0 to 20; m+n is greater than 0; r is 1 to 3; ais 0 or 1; p is independently 0 to 2; provided that a is 0 when r is 3;each R¹ is independently a linear or branched alkyl group having 5 to 29carbons optionally comprising at least 1 unsaturated bond; each R² isindependently —H, or a linear or branched alkyl group having 6 to 30carbons optionally comprising at least 1 unsaturated bond; provided whenFormula (Ia) is chosen, then at least one R is —H and at least two Rgroups are a —R¹; —C(O)R¹; —(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; each R⁴ is independently —H, alinear or branched alkyl group having 6 to 30 carbons optionallycomprising at least 1 unsaturated bond, or combinations thereof;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; provided when Formula (Ib) ischosen, then at least one R or R⁴ is —H; and at least two of R or R⁴ area linear or branched alkyl group optionally comprising at least 1unsaturated bond, or combinations thereof;—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹; and each R¹⁹ is —H, —C(O)R¹, or—CH₂C[CH₂OR]₃, provided when Formula (Ic) is chosen, then at least oneR¹⁹ or R is —H; and at least two of R¹⁹ or R are —C(O)R¹,—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)R²; or—(CH₂CH₂O)_(n)(CH(CH₃)CH₂O)_(m)C(O)R¹.
 14. The method of claim 12,further comprising the step of heating the partially or completelytreated carpet.
 15. The method of claim 12, further comprising the stepof solidifying the coating by drying, cooling, or allowing to cool. 16.The method of claim 12, where the contacting step occurs by spraying,rolling, padding, brushing, sprinkling, dipping, dripping, tumbling, orscreen printing.